new jebsey



Patented-Jan. 192,9.

- UNITED STATES PATENT-OFFICE...

ma masts PAUL, or nae-exam, NEW 103x, ASSIGNOR 'ro METAL a CORPORATION, on mammalian, NEW JERSEY, n coarcna rron or .NEW

raocnss non nncovnnms vananrum.

No Drawing. I

This invention relates to the recovery ofvanadium; and it comprisesa simple and direct method of extracting vanadium from complex ores, wherein the :ore is mixed with hydrated alkali'metal sulfid; the mixture melted'in its water of crystallization and heated until the water is exp leached; the leachings' purified by an adelled; the vmelt dition of an aluminum compound followed partial acidification to precipitate phosb phorous as aluminum phosphate enclosing:

' and carrying down colloidal sulfur, and filtration; and the vanadium compounds- *fdirectly precipitated from the filtrate, 1' usually by an addition of an iron salt inj manipulation. Manymethodshave .been' proposed andgused for this purpose but they -mo stly involve complicated procedures or sideratumto the presence of an oxidizing'agent; all as product with e of expense and tgive lmpure products. Eflicient extraction hard to securely Sometimes the-ore is subjected to smelting treatments followed by [wet treatments; sometimes-theme is extracted with acids and the solutions subyglected to various precipitatingoperations.

- he marketable form in whi'ch the vanadium -is regained, was formerl'y --}generally am- "l'fterials which can be-used making other vanadium compounds or directly used m ferrovanadium. ;-;For this -pur-' urposes; .it' is desirable to obtain a vana ium product,-such as the ferric vanadate,

'm'onium vanadate, but now more oiten ferric vanadate and/or; vanad c oxide,:;m'a-

generally for all metallurgical 'vanadic oxide,etc., as free as-may' beef phosphorous and sulfur aswell'as certain other impurities. Natural ores containing vanadium usually contain not only. phas phorous and sulfur but many other bodies in];

' greater or less amount, such as'mol bdenum;

lead, copper, antimony, iron, ni e1, zinc.

silica, etc. v

Good extraction of vanadium be ob tainedby an alkaline treatmentjof its ores,

using caustic alkali, carbonated-alkali or alkaline sulfids, either in the'dry or the wet vway; and many methods on such reiafineness at least .as'

gterial; .Anhy ens commerci ;A pp1icationsfi1ed a gust 12, 1926. Seriai No. 128,913.

actions have been proposedfsome use. Working with solutions under pres. sure has been proposed. Caustic and carbonat'ed alkalis however not only extract vanadium, but bring into solution; various 1 undesirable bodies, notably phosphorous,

silica, etc. Phosphorous has many analogies with vanadium and is difficult to'separate therefrom with the completeness desirable for many purposes, and particularly where the final product is to be ferrovanadium.

.Alkaline sulfids give an excellent extraction and haveflthe additional advantage-of -dis-' solving-less-other matters; most of the heavy metals remaining undissolved as heavy inetal sulfids. Commercial .alkali sulfids 9 1 generally contain-excess sulfur and this sulr may :be separated the free form in the Where 'thisisrdone, it goes down in colloidal jorm hard to separate. 1 Free suliur in .:the final-j product as-phosphorous. o

It is the. objegct of the present invention to provide-a method whereby I can extract vanadium fromtheseorcs in merchantable' (operations subsequent to the extraction.

f "is asdisadvantageous to form by a low-temperature heating opera- I tion, leaching, purification and precipitation; without the necessity for the use of -pressure or" complicated apparatus.- A fsimple open ironkettleor, panmay be used fort-the heating operatiom- In my rocess, 'I'i'react on the with hydrated a kali 'metalsul-T "fids; mixing the ore. andithe sulfid 'andheating till thesulfid firstmelts in its water of diydraficm,andthen dries up. The melt: is"

thendeachedand the leachingspu-rifiedand vanadiumfiecovered, by precipitation. v.

I Advantageonsly the ore powdered to I great as 100 mesh per' cent amesh sieve) and, it may be much No high temperature and the operation siin 1y consists m p orexand the .and' heating highencii h to melt theh drated ma :rorm of may-be used and in event enough water is added-to correspond-.7 roughly with the water of crystallization of :the crystallized forms. The heatingis continued the mass upfty: low i 'of'water. In so doing, there good-ex, of vanadium which convertedinto a soluble form, but relatively I little'silica goes into solution en=. subsequent.

the phosphorus present as determined by thrown down. The precipitate should be'- white. The addition of acid results in the 'tains-bnt little silica.'

I have found that this solution can be efleaching Practically all the heavy-metals other than vanadium are converted into in-- soluble forms. The extract formed on leachs ing is relatively pure, containing but little in solution other than vanadium; this'vana dium being in the form ofa compound with thesulfurand-the alkali. The solution can'- fectively purified of phosphorus by an addition of a solution of aluminum sulfate or another aluminum compound. The aluminum sulfate is added in the proportion re-' quired to form aluminum phosphate from analysis. Before or after the addition, the solution is acidified to the extent necessary to. allow precipitation of the aluminum phosphate,- but not to the extent where vanadium-sulfur compounds will likewise be formation of H S and more or lessncolloidal sulfur; but the surfur is enclosed and carried down by the gelatinous phosphate and I does not go forward to contaminate the filtrate. The precipitate is readily filtered and washed,' giving a filtrate containing vanadium in relatively pure form.- From this filtrate vanadium can be recovered in an desired form by appropriate treatment;

eit er as. ammonium vanadate, calcium vanadate,"vanad1c oxide, ferrlc vanadatcetc. Ordinarily, I make-ferric vanadatc,

since not only is it a desirable market material but the solution madeby the present method is well adapted for its production.

In operating according to the present invention, I heat-finely powdered vanadium ore, which may be'of any character but is usually a complex ore containing lead and zinc, etc. with commercial hydrated. sodium sulfid. This may be'the mono-sulfid or it may, and usually does, contain-additional sulfur; that is, is a polysulfid. The crystallized sulfid' and the ore may be directly mixed and then heated, or the sulfid may 'first be, melted and then .the'ore stirred in.

In' either case,'th'e mixture is kept stirred for a time at thetemperature at which the. sulfid melts in its water of crystallization.

Heating and stirring are continued until the water ofcrystallization is driven off and a dry pulverulent product results. The whole operation may he conducted in an ordinary open iron kettle with a stirring device. The melt is cooled and leached withwater. This brings the vanadium into solution as a soluble sulfur compound of sodium-and-vanadium, while most of the heavy metals present remainbehind as insoluble sulfids. The leachings are a tolerably pure solution. To this solution I'add a solution of a soluble aluminum compound such as alum or aluminum sulfate in amount equivalent to.

the :1 0 in solution as determined by anali sis. I then add a-littl e acid, Jwhich may be commercial hydrochloric acid or sulfurifacid, to-reduce the alkalinity of the solution andpermit deposition of a gelat inous precipitate of aluminum phosphate, together witlrthe formation of colloidal sulfur. The precipitation is preferential and substantially no V is carried down with theP. 1

In making ferric vanadate, after :filtra-f tion the liquid is treated with a soluble iron I salt, such as ferrous sulfate, and is then.

oxidized in any convenient way to convert the vanadium compounds in solution into the pentavalent form- (V 0 this going down as insoluble ferric vanadate.- -Oxidation may be-etfected by bromin, blowingin chlorin," or. bythe use of chlorates, nitrates, etc, with suflicient acidto develop oxidation. The-insoluble ferric vanadate formed is collected by filtration, -washed, dried and calcined. -'It is a commercial articleand is saleable as such. Y 1

Ot, er insoluble'vana'clium compounds may line sulfids. An in such use, it has the great additional advantageof disposing of free sulfur. v

What I claim is.: 1. In the recovery ofvanadium from its ores, the process which comprises heating such an ore 1n :1. finely dlvided state in ad- 11omixture with a hydrated alkali metal sulfid till the latterfirst melts in its water of crystallization and then solidifies by lossof water.

- 2 In the recovery of 'vanadium'from its ores, the process which comprises heating such an orein a finely divided state in admixt re with a hydrated alkali metal sulfid till t e latter firstmelts in its water of crystallizfation and then drie s'up, cooling and leaching the melt, and adding to the leachings a solution of an aluminum salt amount equivalent to the phos horus present together with enough aci .to form a gela inous p vecipitate of aluminum phos-- 3. In 'the removal of phosphorus from alkaline vanadium solutions made by leaching treated ore, the process which comprises adding-a solution of an aluminum salt in amount equivalent to the phosphorus pres-- ent and acidifying sufl iciently to develop a precipitate of aluminum phosphate.

4. In the recovery of vanadium from its ores, the process which comprises heating such an ore in a finely divided state in the presence of a hydrated alkali metal s'ulfid till the latter first melts in its water of crystallization and then solidifies by loss of Water, leaching the melt so formed, removing phosphorus and sulfur from the alkaline vanadium-containing solution and recovering vanadium from such solution by a precipitation in the presence of an oxidizing agent. p

In testimony whereof I ailix my signature.

ma MARGIE PAUL. 

